Process for the preparation of artificial resins and oleoresins



, iatented-Oct. Z, 1923.

To all whom it may concern:

stairs PATENT. OFFICE.

HENRI wUY'rs, or BRUSSELS, BELGIUM.

- rnocnss roa'rnn ranrnaanon'or' ARTIFICIAL Resins AND OLEORESINS.

Drawing.

Be it known that I, HENRI WUY'rs, a-sub ect of the King of the Belgians,residing at russels, in the Kingdom of Belgium, have .invented certainnew and useful Improvements in Processes for the Preparation ofArtificial- Resins and Oleoresins, of which the following is aspecification.

The present invention is a process for the preparation of artificialresins and oleoresins for use in various industries notably in thepreparation of varnishes, lacquers,

insulators, and mixtures i tended for impermeability purposes, and.antiseptics or emulsions capable of various uses such as de asing andcleaning. 5

action, aided by a catalyzer, of phenols (and naphthols) with terpenehydrocarbons such as terebenthine and other essential oils or portionsthereof or s nthetic products based on the non-saturate hydrocarbons offormula (l H g.

The artificial resins and 'oleoresins thus obtained are composed ofethers of phenol P in the nucleus an eventually by products ofpolymerization of the terpene hydrocarbons.

To carry out the invention practically the particular catalyzer whichw1ll bring about the desired reaction must be chosen amongst a. Thestron acids such as hydrochloric, h drobromic, ydriodic, hydrofluoric,sulp uric, nitric, phosphoric (and its 'anhy-, dride), oxalic sulphonic,(in particular paratoluene-su honic) acids.

1).. Certain sa ts such as anhydrous aluminium chloride, anhydrousferric chloride, zincchloride, certain silicates, certain silicated orsiliceous earths suitably prepared, such as Florida earth (floridine orfullers earthf, etc.

c. Certain'substances such as chlorine, bromine, iodine.

According to the invention the nature of the catalyzer, the temperatureof the reaction the relative proportions of the reacting substance canbe varied se arately or simultaneously to bring about t e orientation ofthe reaction for preparing sufi'icientquantities of the comoundshereinbe'fore referred to and eventu Fly for the exclusiveproduction of one of them. In this way it is pos- 1s process conslstsessentially in the rehenols ethe'rified by terpene radicles) of enolshaving to one radicles substituted Application filed August 20, 1921.Serial No. 493,939.

sible, in certain cases, to prepare individual substances, and, in allcases to obtain directly, or after selection by treatment with steam ordistillation in vacuo, solid resins or oleoresins of greatly varyingconsistency according to. the mode of preparation.

As an exampleof the preparation of an ether of phenol reference may-bemade to the action of carvene upon naphthol.

The lnitialtemperature of their-equimolecular mixture being about 100 C.the

addition of a small. quantity of paratoluene sulphonic acid brings abouta considerable rise of =tem erature. This is maintained below 160 (J.Treatment with steam in the presence of a little sodium carbonate eliminates the sulphonic acid theihydrocarbon and the naphthol not beingchanged are distilled; the residual oil is insoluble in the alkalis;distilled under a very reduced p'res-.

sure it shows a constant boiling point; it is an ether of phenol of the,formula io r io n' pene phenols in considerable quantity reference maybe made to the reaction of equimolecular uantities of carvene andordinary phenol in t e presence of 0.2 grams of paratoluene-sulphonicacid.

When the spontaneous heating of the mass from 30 C. has reached 105C.the action is moderated to prevent this temperature being exceeded. Thetreatment with steam takes place as in the preceding case. It isfollowed by a treatment withpotassiufii hydroxide or may be obtainedby'the evaporation of the solvent.

If in the preceding example chloride of zinc be substituted for theparatoluene-sulphonic acid and the mixture be maintained at atemperature of about 100 C. for a period of. 30 hours thephenolficcom'pound obtained is a brittle resin having a considerablhigher melting'point.

he composition of the resins and the oleo- -As an example of thepreparation terresins in oxygen, obtained by the process forming thesubject of the invention enables them to be dissolved in hydrocarbonsolvents and thus permits of the preparation of inexpensive lacquers orvarnishes.

In the presence of alkalis or even small quantities of alkalinecarbonates, these resins I and oleoresins, as alsothe non-selectedmixtures obtained directly by the action of the catalyzers upon thephenols and terpene hydrocarbonscan be emulsified with water to 1 ofresins, such as toluene;

eventually utilized for the purpose of de- 'the temperature below 160produce extremely stable emulsions. These emulsions are formed even inthe presence greasing and cleanin What I, claim. is: 1. A process ofpreparing artificial resins and oleoresins the said process consistingThey can be 3. A process of preparing an ether of phenol said processconsistin in causing carvene to react; with napht ol in equimolecularquantity by the addition of paratoluene-sulphonic acid, maintaining thetemperature below 160 C. then heating with steam, in the presence ofsodium carbonate whereby the sulphonic acid is eliminated and finallydistilling the h drocarbon and the untransformed naphthol a 4. A processor preparing terpene phenols, the said process consisting in causingcarvene to act upon phenol in equimolecular quantity in the presence ofparatoluene-sulphonic acid maintaining the temperature below 105 thentreating with steam and subsequently exhausting with potassium in thepresence of a solvent at about 70-80 (Land finally separating the twoliquid layer-s whereby the alkaline liquors obtained yield the terpenephenols on solidification. I

In testimon whereof I have afiixed my signature in t e presence oftwowitnesses.

a temperature of

